Title of Invention: Olefin-based copolymer and manufacturing method thereof
technical field
[One]
Cross-Citation with Related Applications
[2]
This application claims the benefit of priority based on the Korean patent application 2019-0105771 dated August 28, 2019, and all contents disclosed in the documents of the Korean patent applications are incorporated as a part of this specification.
[3]
technical field
[4]
The present invention relates to an olefin-based copolymer having improved physical properties such as hardness, flexural strength, and tear strength while having high fluidity by having a soluble fraction at a low temperature having a high weight average molecular weight, and a method for preparing the same.
[5]
background
[6]
Olefin polymerization catalyst systems can be classified into Ziegler-Natta and metallocene catalyst systems, and these two highly active catalyst systems have been developed according to their respective characteristics. Ziegler-Natta catalyst has been widely applied to existing commercial processes since its invention in the 1950s. There is a problem in that there is a limit in securing the desired physical properties because the composition distribution is not uniform.
[7]
The metallocene catalyst consists of a combination of a main catalyst containing a transition metal compound as a main component and a cocatalyst containing an organometallic compound containing aluminum as a main component, and this catalyst is a homogeneous complex catalyst and is a single site catalyst. A polymer with a narrow molecular weight distribution and a uniform comonomer composition distribution is obtained according to the single active site characteristic, and the stereoregularity of the polymer, copolymerization characteristics, molecular weight, crystallinity, etc. has properties that can change it.
[8]
On the other hand, linear low-density polyethylene is produced by copolymerizing ethylene and alpha olefin at low pressure using a polymerization catalyst, and is a resin having a narrow molecular weight distribution, short-chain branches of a constant length, and no long-chain branches. The linear low-density polyethylene film has high breaking strength and elongation along with the characteristics of general polyethylene, and has excellent tear strength and drop impact strength. are doing
[9]
However, most of the linear low-density polyethylene using 1-butene or 1-hexene as a comonomer is produced in a single gas phase reactor or a single loop slurry reactor, and the productivity is high compared to the process using 1-octene comonomer, but these products are also used Due to limitations in catalyst technology and process technology, physical properties are significantly inferior to those when 1-octene comonomer is used, and the molecular weight distribution is narrow, resulting in poor processability.
[10]
In US Patent No. 4,935,474, two or more metallocene compounds are used to report a polyethylene production method having a broad molecular weight distribution. U.S. Patent No. 6,828,394 reports on a method for producing polyethylene, which has excellent processability and is particularly suitable for films, by using a mixture of those having good comonomer binding properties and those not having good comonomer binding properties. In addition, in U.S. Patent Nos. 6,841,631 and 6,894,128, polyethylene having a bicrystalline or polycrystalline molecular weight distribution is prepared with a metallocene-based catalyst using at least two metal compounds, and is used in films, blow molding, pipes, etc. reported to be applicable. However, these products have improved processability, but the dispersion state by molecular weight within the unit particles is not uniform, so the extrusion appearance is rough and the physical properties are not stable even under relatively good extrusion conditions.
[11]
Against this background, there is a constant demand for the production of better products with a balance between physical properties and processability, and in particular, the need for an olefin-based copolymer having excellent processability is further demanded.
[12]
[13]
[Prior art literature]
[14]
[Patent Literature]
[15]
(Patent Document 1) US Patent No. 4,935,474
[16]
(Patent Document 2) US Patent No. 6,828,394
[17]
(Patent Document 3) US Patent No. 6,841,631
[18]
(Patent Document 4) US Patent No. 6,894,128
[19]
DETAILED DESCRIPTION OF THE INVENTION
technical challenge
[20]
An object of the present invention is to provide an olefin-based copolymer having improved physical properties such as flexural strength and tensile strength while having high fluidity by exhibiting a high weight average molecular weight of a soluble fraction at a low temperature.
[21]
Another object of the present invention is to provide a method for preparing the olefin-based copolymer.
[22]
means of solving the problem
[23]
The present invention (a) melt index (Melt Index, MI, 190 ℃, 2.16 kg load condition) is 10 to 100 g / 10 minutes, (b) cross-fractionation chromatography (Cross-Fractionation Chromatography; CFC) - The soluble fraction (SF) at 20 ° C. is 0.5 to 10 wt%, the weight average molecular weight (Mw (SF)) of the soluble fraction is 22,000 or more, (c) the weight average molecular weight of the olefinic copolymer ( Mw) and the ratio of the weight average molecular weight (Mw(SF)) of the soluble fraction, Mw:Mw(SF), has a value of 0.9: 1 to 2: 1, providing an olefin-based copolymer.
[24]
In addition, the present invention provides a step of polymerizing the olefinic monomer by adding hydrogen at a rate of 10 to 100 cc/min in the presence of a catalyst composition comprising a transition metal compound represented by the following Chemical Formula 1; A method for producing a composite is provided.
[25]
[Formula 1]
[26]

[27]
In Formula 1,
[28]
R 1 is hydrogen; alkyl having 1 to 20 carbon atoms; alkenyl having 2 to 20 carbon atoms; alkoxy having 1 to 20 carbon atoms; aryl having 6 to 20 carbon atoms; arylalkoxy having 7 to 20 carbon atoms; alkylaryl having 7 to 20 carbon atoms; or arylalkyl having 7 to 20 carbon atoms;
[29]
R 2 and R 3 are each independently hydrogen; halogen; alkyl having 1 to 20 carbon atoms; alkenyl having 2 to 20 carbon atoms; arylalkyl having 7 to 20 carbon atoms; alkylamido having 1 to 20 carbon atoms; or arylamido having 6 to 20 carbon atoms,
[30]
R 4 to R 9 are each independently hydrogen; silyl; alkyl having 1 to 20 carbon atoms; alkenyl having 2 to 20 carbon atoms; aryl having 6 to 20 carbon atoms; alkylaryl having 7 to 20 carbon atoms; arylalkyl having 7 to 20 carbon atoms; or a metalloid radical of a Group 14 metal substituted with hydrocarbyl having 1 to 20 carbon atoms,
[31]
Two or more adjacent to each other among R 2 to R 9 may be connected to each other to form a ring,
[32]
Q is Si, C, N, P or S;
[33]
M is a group 4 transition metal,
[34]
X 1 and X 2 are each independently hydrogen; halogen; alkyl having 1 to 20 carbon atoms; alkenyl having 2 to 20 carbon atoms; aryl having 6 to 20 carbon atoms; alkylaryl having 7 to 20 carbon atoms; arylalkyl having 7 to 20 carbon atoms; alkylamino having 1 to 20 carbon atoms; or arylamino having 6 to 20 carbon atoms.
[35]
Effects of the Invention
[36]
The olefin-based copolymer according to the present invention has a high weight average molecular weight with a soluble fraction at a low temperature, and has improved hardness, high fluidity, and impact strength at low temperature and room temperature compared to a copolymer having the same level of density and strength. There is an advantage of being able to produce improved superior composites.
[37]
Modes for carrying out the invention
[38]
Hereinafter, the present invention will be described in more detail to help the understanding of the present invention.
[39]
The terms or words used in the description and claims of the present invention should not be construed as being limited to their ordinary or dictionary meanings, and the inventor appropriately defines the concept of the term in order to best describe his invention. Based on the principle that can be done, it should be interpreted as meaning and concept consistent with the technical idea of ​​the present invention.
[40]
In the present invention, the term "polymer" means a polymer compound prepared by polymerization of monomers of the same or different types. The generic term "polymer" includes the terms "homopolymer", "copolymer", "terpolymer" as well as "interpolymer". Also, the term “interpolymer” refers to a polymer prepared by polymerization of two or more different types of monomers. The generic term "interpolymer" refers to the term "copolymer" (which is commonly used to refer to polymers prepared from two different monomers), as well as the term "copolymer" (usually used to refer to polymers prepared from three different types of monomers). used) the term "terpolymer". It includes polymers prepared by polymerization of four or more types of monomers.
[41]
[42]
Hereinafter, the present invention will be described in detail.
[43]
[44]
Olefin-based copolymer
[45]
The olefin-based copolymer according to the present invention is characterized in that the following conditions (a) to (c) are satisfied.
[46]
(a) melt index (Melt Index, MI, 190 ℃, 2.16 kg load condition) is 10 to 100 g / 10 minutes,
[47]
(b) the soluble fraction (SF) at -20 °C measured by cross-fractionation chromatography (CFC) is 0.5 to 10 wt%, and the weight average molecular weight (Mw(SF) of the soluble fraction )) is greater than or equal to 22,000,
[48]
(c) The ratio of the weight average molecular weight (Mw) of the olefin-based copolymer to the weight average molecular weight (Mw (SF)) of the soluble fraction Mw:Mw(SF) has a value of 0.9:1 to 2:1.
[49]
[50]
According to the condition (a), the melt index (Melt Index, MI, 190 ℃, 2.16kg load condition) of the olefin-based copolymer according to the present invention is 10 to 100 g/10 min.
[51]
The melt index (MI) can be adjusted by controlling the amount of comonomer used in the catalyst used in the process of polymerizing the olefin-based copolymer, and the mechanical properties and impact strength of the olefin-based copolymer, and the moldability affect The melt index is measured at 190° C. under a load condition of 2.16 kg according to ASTM D1238 under low density conditions, and may be 5 to 200 g/10 min, specifically 10 to 150 g/10 min, more specifically 10 to 100 g It can be /10 minutes. Specifically, the melt index may be 10 g/10 min or more, or 11 g/10 min or more, 11.5 g/10 min or more, or 12 g/10 min or more, and 100 g/10 min or less, 50 g/10 min or more. min or less, or 40 g/10 min or less, 36 g/10 min or less.
[52]
[53]
According to the condition (b), the olefin-based copolymer according to the present invention has a soluble fraction (SF) of 0.5 to 10 weight at -20°C measured by cross-fractionation chromatography (CFC). %, and the weight average molecular weight (Mw (SF)) of the soluble fraction is 22,000 or more.
[54]
The Cross-Fractionation Chromatography (CFC) is a method combining Temperature Rising Elution Fractionation (TREF) and Gel Filtration Chromatography (GPC). The crystallinity distribution and the molecular weight distribution can be known at the same time.
[55]
Specifically, a high-temperature sample solution in which the olefin-based copolymer is completely dissolved in a solvent is injected into a column filled with an inert carrier, the temperature of the column is lowered to attach the sample to the surface of the filler, and then ortho dichlorobenzene is introduced into the column. The temperature of the column is gradually increased while flowing The concentration of the olefinic copolymer eluted at each temperature is detected, and the component eluted at each temperature is sent to GPC online for each fraction at the same time to obtain a chromatogram, and the molecular weight distribution of each component is calculated from this. .
[56]
In addition, since the higher the crystallinity of the eluted component, the higher the elution temperature. Thus, the crystallinity distribution of the olefinic copolymer can be known by finding the relationship between the elution temperature and the elution amount (wt%) of the olefinic copolymer.
[57]
In the olefin-based copolymer of the present invention, the fraction soluble at -20°C measured by CFC may be 0.5 to 20% by weight, preferably 0.5 to 15% by weight, or 0.5 to 10% by weight. Specifically, the soluble fraction at -20 °C measured by CFC may be 0.5 wt% or more, or 1 wt% or more, 2 wt% or more, and 10 wt% or less, 8 wt% or less, 8 wt% or less, 7 weight percent or less, or 6 weight percent or less.
[58]
[59]
In addition, while satisfying the content of the soluble fraction at -20 ° C., the weight average molecular weight (Mw (SF)) of the soluble fraction may be 22,000 or more, preferably 23,000 or more, more preferably 25,000 or more. In addition, the weight average molecular weight (Mw (SF)) of the soluble fraction may be 60,000 or less, 60,000 or less, 50,000 or less, 50,000 or less, 45,000 or less, 43,000 or less, or 40,000 or less.
[60]
[61]
It is known that the olefin-based copolymer eluted at a low elution temperature is a low crystalline copolymer with a low stereoregularity, a high comonomer content, and a low density. In particular, as measured in the present invention, the fraction soluble at -20 ° C. is a component with extremely low crystallinity and is often referred to as an ultra-low crystallinity region because of its strong amorphous properties. In general polymerization, when the copolymerizability is extremely increased, the molecular weight of the polymer is decreased in inverse proportion. As a result, the ultra-low crystallinity soluble fraction eluted at -20°C or lower generally has a very small molecular weight compared to the total olefin-based copolymer.
[62]
On the other hand, the soluble fraction at -20°C has a very low density and excellent elasticity due to its ultra-low crystallinity, and thus has the effect of improving the impact strength when manufactured as a polypropylene-based composite material. On the other hand, in terms of molecular weight, since the molecular weight compared to the molecular weight of the entire olefin-based copolymer is remarkably low, it causes a decrease in mechanical strength such as tensile strength, and there is a problem in that low temperature and high temperature impact strength are weak.
[63]
On the other hand, in the olefin-based copolymer of the present invention, as described above, the content of the soluble fraction at -20 °C measured by CFC accounts for 0.5 to 20 wt%, but various physical properties such as flexural strength and hardness as well as tear strength and tensile strength This is excellent, because the weight average molecular weight of the soluble fraction is 22,000 or more, preferably 23,000 or more, and more preferably 25,000 or more, indicating a high value.
[64]
[65]
According to the condition (c), Mw, which is the ratio of the weight average molecular weight (Mw) to the weight average molecular weight (Mw (SF)) of the soluble fraction in the olefinic copolymer according to the present invention: The value of Mw (SF) is 0.9 : 1 to 2 : 1.
[66]
As described above, in the olefin-based copolymer of the present invention, the weight average molecular weight of the soluble fraction at -20 ° C as measured by CFC is 20,000 or more, preferably 22,000 or more, more preferably 25,000 or more. Rather, even when compared to the total weight average molecular weight (Mw) of the olefin-based copolymer, the distribution of molecular weight is high, regardless of crystallinity, so that the value of Mw: Mw (SF) satisfies 0.9: 1 to 2: 1. can be considered uniform. As such, the molecular weight of the ultra-low crystallinity region, which is the fraction soluble at -20 ° C, maintains a similar level compared to the total molecular weight, so that it has an impact strength equivalent to that of the existing olefin-based copolymer and has excellent mechanical properties such as tensile strength. will appear
[67]
The value of Mw: Mw (SF) is 0.9: 1 to 2: 1, preferably 1:1 to 2: 1, and the higher the ratio of Mw to Mw (SF), the lower the temperature of the olefin-based copolymer. and high temperature impact strength will also be improved.
[68]
[69]
In addition, the olefin-based copolymer of the present invention exhibits a low density of 0.85 g/cc to 0.89 g/cc when measured according to ASTM D-792, specifically 0.855 to 0.89 g/cc, more specifically 0.86 to 0.89 g/cc can have a density of That is, the olefin-based copolymer according to the present invention may be a low-density olefin-based copolymer having a low density in the above range while satisfying the conditions (a) to (c) as described above, but the density value is limited thereto no.
[70]
In addition, the olefinic copolymer of the present invention may have a weight average molecular weight (Mw) of 10,000 to 100,000 g/mol, specifically 20,000 to 80,000 g/mol, and more specifically 20,000 to 70,000 g/mol. mol, or 30,000 to 70,000 g/mol. The weight average molecular weight (Mw) is a polystyrene equivalent molecular weight analyzed by gel permeation chromatography (GPC).
[71]
In addition, the olefin-based copolymer of the present invention may have a molecular weight distribution (MWD) of 1.5 to 3.0, which is a ratio (Mw/Mn) of a weight average molecular weight (Mw) to a number average molecular weight (Mn), specifically may be 1.5 to 2.8, more specifically 1.9 to 2.5.
[72]
The olefin-based copolymer of the present invention may have a hardness (Shore A) of 30 to 80, specifically 40 to 80, and more specifically 50 to 80. The olefin-based copolymer may exhibit a high hardness (Shore A) when it has a similar level of density and melt index compared to a conventional conventional olefin-based copolymer, and thus improved tear strength, tensile strength, elongation, It may have flexural strength and the like.
[73]
As will be described later, the olefin-based copolymer of the present invention may be an olefin-based copolymer prepared by using a transition metal compound represented by Formula 1 as a catalyst and introducing a specific amount of hydrogen to cause a polymerization reaction, such as By being prepared by the manufacturing method, the weight average molecular weight value of the soluble fraction at -20 ° C is higher than that of the conventional olefin-based copolymer, and physical properties such as improved tear strength, tensile strength, elongation, and flexural strength can be exhibited.
[74]
[75]
The olefin-based copolymer of the present invention is a copolymer of two or more selected from an olefin-based monomer, specifically an alpha-olefin-based monomer, a cyclic olefin-based monomer, a diene olefin-based monomer, a triene olefin-based monomer, and a styrene-based monomer and, specifically, may be a copolymer of ethylene and an alpha-olefinic monomer having 3 to 12 carbon atoms, or a copolymer of ethylene and an alpha-olefinic monomer having 3 to 10 carbon atoms. Specifically, the olefin-based copolymer of the present invention may be a copolymer of ethylene and propylene, ethylene and 1-butene, ethylene and 1-hexene, ethylene and 4-methyl-1-pentene, or ethylene and 1-octene.
[76]
The alpha-olefinic monomer is propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-heptene, 1-octene, 1-decene, 1-undecene, 1-dodecene , 1-tetradecene, 1-hexadecene, 1-eicosene, norbornene, norbornadiene, ethylidenenorbornene, phenylnorbornene, vinylnorbornene, dicyclopentadiene, 1,4-butadiene, 1,5 It may include at least one member selected from the group consisting of -pentadiene, 1,6-hexadiene, styrene, alpha-methylstyrene, divinylbenzene, and 3-chloromethylstyrene, but is not limited thereto.
[77]
[78]
The olefinic copolymer of the present invention may be prepared through a continuous solution polymerization reaction in which hydrogen is continuously added in a single reactor in the presence of a metallocene catalyst composition containing one or more transition metal compounds and polymerized olefinic monomers. .
[79]
The olefin-based copolymer according to the present invention may be one selected from the group consisting of a random copolymer, an alternating copolymer, and a graft copolymer, and more specifically, a random copolymer. can
[80]
[81]
Method for producing an olefin-based copolymer
[82]
The method for preparing the olefin-based copolymer of the present invention comprises the steps of polymerizing the olefin-based monomer by adding hydrogen at a rate of 10 to 100 cc/min in the presence of a catalyst composition comprising a transition metal compound represented by the following formula (1); characterized by including.
[83]
[Formula 1]
[84]

[85]
In Formula 1,
[86]
R 1 is hydrogen; alkyl having 1 to 20 carbon atoms; alkenyl having 2 to 20 carbon atoms; alkoxy having 1 to 20 carbon atoms; aryl having 6 to 20 carbon atoms; arylalkoxy having 7 to 20 carbon atoms; alkylaryl having 7 to 20 carbon atoms; or arylalkyl having 7 to 20 carbon atoms;
[87]
R 2 and R 3 are each independently hydrogen; halogen; alkyl having 1 to 20 carbon atoms; alkenyl having 2 to 20 carbon atoms; arylalkyl having 7 to 20 carbon atoms; alkylamido having 1 to 20 carbon atoms; or arylamido having 6 to 20 carbon atoms,
[88]
R 4 to R 9 are each independently hydrogen; silyl; alkyl having 1 to 20 carbon atoms; alkenyl having 2 to 20 carbon atoms; aryl having 6 to 20 carbon atoms; alkylaryl having 7 to 20 carbon atoms; arylalkyl having 7 to 20 carbon atoms; or a metalloid radical of a Group 14 metal substituted with hydrocarbyl having 1 to 20 carbon atoms,
[89]
Two or more adjacent to each other among R 2 to R 9 may be connected to each other to form a ring,
[90]
Q is Si, C, N, P or S;
[91]
M is a group 4 transition metal,
[92]
X 1 and X 2 are each independently hydrogen; halogen; alkyl having 1 to 20 carbon atoms; alkenyl having 2 to 20 carbon atoms; aryl having 6 to 20 carbon atoms; alkylaryl having 7 to 20 carbon atoms; arylalkyl having 7 to 20 carbon atoms; alkylamino having 1 to 20 carbon atoms; or arylamino having 6 to 20 carbon atoms.
[93]
[94]
The transition metal compound of Formula 1 described herein is a cyclopentadiene in which benzothiophene is fused by a cyclic bond, and an amido group (NR 1 ) is stably formed by Q (Si, C, N or P). It is crosslinked and forms a structure in which the Group 4 transition metal is coordinated.
[95]
When the catalyst composition is used for polymerization of an olefinic monomer, it is possible to produce a copolymer having characteristics such as high activity, high molecular weight, and high copolymerizability even at a high polymerization temperature. In particular, the transition metal compound of Formula 1 has an ultra-low density of less than 0.910 g/cc because a large amount of alpha-olefin as well as a linear low-density polyethylene having a level of 0.85 g/cc to 0.93 g/cc can be introduced due to structural characteristics. It is also possible to prepare polymers (elastomers) of the region.
[96]
In addition, in the present invention, an olefin-based copolymer is prepared by polymerizing the olefin-based monomer by adding hydrogen at 10 to 100 cc/min while using the catalyst of the transition metal compound represented by Chemical Formula 1, and does not correspond to Chemical Formula 1 As described above, the weight average molecular weight of the soluble fraction at low temperature is higher than that of the olefin-based copolymer prepared by polymerizing a monomer without using a transition metal compound or adding hydrogen, and tear strength, tensile strength, elongation, etc. An olefin-based copolymer having excellent physical properties can be prepared.
[97]
[98]
In Formula 1, R 1 is hydrogen; alkyl having 1 to 20 carbon atoms; alkoxy having 1 to 20 carbon atoms; aryl having 6 to 20 carbon atoms; arylalkoxy having 7 to 20 carbon atoms; alkylaryl having 7 to 20 carbon atoms; Or it may be an arylalkyl having 7 to 20 carbon atoms. Preferably, the R 1 is alkyl having 1 to 20 carbon atoms; aryl having 6 to 20 carbon atoms; arylalkoxy having 7 to 20 carbon atoms; Or it may be an arylalkyl having 7 to 20 carbon atoms, more preferably, methyl, ethyl, propyl, butyl, isobutyl, tibutyl, isopropyl, cyclohexyl, benzyl, phenyl, methoxyphenyl, ethoxyphenyl, fluorine phenyl, bromophenyl, chlorophenyl, dimethylphenyl or diethylphenyl.
[99]
In Formula 1, R 2 and R 3 are each independently hydrogen; alkyl having 1 to 20 carbon atoms; aryl having 6 to 20 carbon atoms; Or it may be an alkylaryl having 6 to 20 carbon atoms, preferably, the R 2 and R 3 are each independently hydrogen; alkyl having 1 to 20 carbon atoms; Or it may be an aryl having 6 to 20 carbon atoms.
[100]
In Formula 1, R 4 To R 9 Are each independently hydrogen; alkyl having 1 to 20 carbon atoms; aryl having 6 to 20 carbon atoms; alkylaryl having 7 to 20 carbon atoms; Or it may be an arylalkyl having 7 to 20 carbon atoms.
[101]
In Formula 1, R 4 And R 5 Are the same as or different from each other, and each independently, alkyl having 1 to 20 carbon atoms; Or it may be an aryl having 6 to 20 carbon atoms.
[102]
In Formula 1, R 4 and R 5 may be the same as or different from each other, and each independently may be an alkyl having 1 to 6 carbon atoms.
[103]
In Formula 1, R 4 and R 5 may be methyl, ethyl, or propyl.
[104]
In Formula 1, R 6 To R 9 Are the same as or different from each other, and each independently, hydrogen; alkyl having 1 to 20 carbon atoms; aryl having 6 to 20 carbon atoms; alkylaryl having 7 to 20 carbon atoms; Or it may be an arylalkyl having 7 to 20 carbon atoms.
[105]
In Formula 1, R 6 To R 9 Are the same as or different from each other, and each independently, hydrogen; or alkyl having 1 to 20 carbon atoms.
[106]
In Formula 1, R 6 To R 9 Are the same as or different from each other, and each independently, may be hydrogen or methyl.
[107]
In Formula 1, M may be Ti, Hf, or Zr.
[108]
In Formula 1, X 1 and X 2 may be the same as or different from each other, and each independently hydrogen, halogen, an alkyl group having 1 to 20 carbon atoms, or alkenyl having 2 to 20 carbon atoms.
[109]
[110]
Preferably, the R 1 is hydrogen; alkyl having 1 to 20 carbon atoms; alkoxy having 1 to 20 carbon atoms; aryl having 6 to 20 carbon atoms; arylalkoxy having 7 to 20 carbon atoms; alkylaryl having 7 to 20 carbon atoms; or arylalkyl having 7 to 20 carbon atoms, wherein R 2 and R 3 are each independently hydrogen; alkyl having 1 to 20 carbon atoms; aryl having 6 to 20 carbon atoms; or an alkylaryl having 6 to 20 carbon atoms, wherein R 4 to R 9 are each independently hydrogen; alkyl having 1 to 20 carbon atoms; aryl having 6 to 20 carbon atoms; alkylaryl having 7 to 20 carbon atoms; or arylalkyl having 7 to 20 carbon atoms, and two or more adjacent to each other among R 2 to R 9 may be connected to each other to form an aliphatic ring having 5 to 20 carbon atoms or an aromatic ring having 6 to 20 carbon atoms, the aliphatic The ring or aromatic ring may be substituted with halogen, alkyl having 1 to 20 carbons, alkenyl having 2 to 20 carbons, or aryl having 6 to 20 carbons, and Q may be Si, C, N or P.
[111]
More preferably, R 1 is alkyl having 1 to 20 carbon atoms; aryl having 6 to 20 carbon atoms; arylalkoxy having 7 to 20 carbon atoms; or arylalkyl having 7 to 20 carbon atoms, wherein R 2 and R 3 are each independently hydrogen; alkyl having 1 to 20 carbon atoms; or aryl having 6 to 20 carbon atoms, wherein R 4 to R 9 are each independently hydrogen; alkyl having 1 to 20 carbon atoms; or aryl having 6 to 20 carbon atoms, and Q may be Si.
[112]
[113]
In addition, the transition metal compound represented by Chemical Formula 1 may be one selected from the group consisting of compounds of Chemical Formulas 1-1 to 1-6, but is not limited thereto, and various compounds within the range defined in Chemical Formula 1 may be used in the present invention. is applicable to
[114]
[Formula 1-1] [Formula 1-2] [Formula 1-3]
[115]

[116]
[Formula 1-4] [Formula 1-5] [Formula 1-6]
[117]

[118]
Each of the substituents used herein will be described in detail as follows.
[119]
In the present invention, the "halogen" means fluorine, chlorine, bromine or iodine.
[120]
In the present invention, the "alkyl" refers to a straight-chain or branched hydrocarbon residue.
[121]
In the present invention, the "alkenyl" refers to a straight-chain or branched alkenyl group. The branched chain is alkyl having 1 to 20 carbon atoms; alkenyl having 2 to 20 carbon atoms; aryl having 6 to 20 carbon atoms; alkylaryl having 7 to 20 carbon atoms; Or it may be an arylalkyl having 7 to 20 carbon atoms.
[122]
In the present invention, the "aryl" preferably has 6 to 20 carbon atoms, and specifically includes phenyl, naphthyl, anthracenyl, pyridyl, dimethylanilinyl, anisolyl, and the like, but is not limited thereto.
[123]
In the present invention, the "silyl" may be a silyl substituted with an alkyl having 1 to 20 carbon atoms, for example, may be trimethylsilyl or triethylsilyl.
[124]
In the present invention, the "alkylaryl" refers to an aryl group substituted by the alkyl group.
[125]
In the present invention, the "arylalkyl" refers to an alkyl group substituted by the aryl group.
[126]
In the present invention, the "alkyl amino" refers to an amino group substituted by the alkyl group, and includes, but is not limited to, a dimethylamino group, a diethylamino group, and the like.
[127]
In the present invention, the "hydrocarbyl group", unless otherwise stated, has 1 carbon number consisting of only carbon and hydrogen regardless of its structure, such as alkyl, aryl, alkenyl, alkynyl, cycloalkyl, alkylaryl or arylalkyl. to 20 monovalent hydrocarbon groups.
[128]
[129]
The transition metal compound represented by Formula 1 may be used alone or in the form of a composition further comprising at least one of the cocatalyst compounds represented by the following Formulas 2 to 4 in addition to the transition metal compound of Formula 1, wherein polymerization of an olefinic monomer It can be used as a catalyst in the reaction. The promoter compound may serve to activate the transition metal compound represented by Chemical Formula 1.
[130]
[Formula 2]
[131]
-[Al(R 10 )-O] a -
[132]
[Formula 3]
[133]
A(R 10 ) 3
[134]
[Formula 4]
[135]
[LH] + [W(D) 4 ] - or [L] + [W(D) 4 ] -
[136]
In Formulas 2 to 4,
[137]
R 10 may be the same as or different from each other, and are each independently selected from the group consisting of halogen, hydrocarbyl having 1 to 20 carbon atoms, and hydrocarbyl having 1 to 20 carbon atoms substituted with halogen,
[138]
A is aluminum or boron,
[139]
D is each independently aryl having 6 to 20 carbon atoms or alkyl having 1 to 20 carbon atoms in which one or more hydrogen atoms may be substituted with a substituent, wherein the substituent is halogen, hydrocarbyl having 1 to 20 carbon atoms, alkoxy having 1 to 20 carbon atoms and at least one selected from the group consisting of aryloxy having 6 to 20 carbon atoms,
[140]
H is a hydrogen atom,
[141]
L is a neutral or cationic Lewis acid,
[142]
W is a group 13 element,
[143]
a is an integer greater than or equal to 2;
[144]
[145]
The compound represented by Formula 2 may be an alkylaluminoxane such as methylaluminoxane (MAO), ethylaluminoxane, isobutylaluminoxane, and butylaluminoxane, and also a modified alkyl in which two or more kinds of the alkylaluminoxane are mixed. It may be aluminoxane, specifically methylaluminoxane, modified methylaluminoxane (MMAO), but is not limited thereto.
[146]
The compound represented by Formula 3 is trimethylaluminum, triethylaluminum, triisobutylaluminum, tripropylaluminum, tributylaluminum, dimethylchloroaluminum, triisopropylaluminum, tri-s-butylaluminum, tricyclopentylaluminum, tri Pentyl aluminum, triisopentyl aluminum, trihexyl aluminum, trioctyl aluminum, ethyl dimethyl aluminum, methyl diethyl aluminum, triphenyl aluminum, tri-p-tolyl aluminum, dimethyl aluminum methoxide, dimethyl aluminum ethoxide, trimethyl boron, triethyl boron, triisobutyl boron, tripropyl boron, tributyl boron, and the like, and specifically, may be trimethyl aluminum, triethyl aluminum, triisobutyl aluminum, and the like, but is not limited thereto.
[147]
The compound represented by Formula 4 is triethylammoniumtetraphenylboron, tributylammoniumtetraphenylboron, trimethylammoniumtetraphenylboron, tripropylammoniumtetraphenylboron, trimethylammoniumtetra(p-tolyl)boron, trimethylammoniumtetra(o ,p-dimethylphenyl)boron, tributylammoniumtetra(p-trifluoromethylphenyl)boron, trimethylammoniumtetra(p-trifluoromethylphenyl)boron, tributylammoniumtetrapentafluorophenylboron, N,N-di Ethylaniliniumtetraphenylboron, N,N-diethylaniliniumtetrapentafluorophenylboron, diethylammoniumtetrapentafluorophenylboron, triphenylphosphoniumtetraphenylboron, trimethylphosphoniumtetraphenylboron, dimethylanilinium Tetrakis(pentafluorophenyl)borate, triethylammoniumtetraphenylaluminum, tributylammoniumtetraphenylaluminum, trimethylammoniumtetraphenylaluminum, tripropylammoniumtetraphenylaluminum, trimethylammoniumtetra(p-tolyl)aluminum, tripropylammonium Tetra(p-tolyl)aluminum, triethylammoniumtetra(o,p-dimethylphenyl)aluminum, tributylammoniumtetra(p-trifluoromethylphenyl)aluminum, trimethylammoniumtetra(p-trifluoromethylphenyl)aluminum, tri Butylammonium tetrapentafluorophenylaluminum, N,N-diethylaniliniumtetraphenylaluminum, N,N-diethylaniliniumtetrapentafluorophenylaluminum, diethylammoniumtetrapentatentraphenylaluminum, triphenylphosphonium Tetraphenylaluminum, trimethylphosphoniumtetraphenylaluminum, tripropylammoniumtetra(p-tolyl)boron, triethylammoniumtetra(o,p-dimethylphenyl)boron, triphenylcarboniumtetra(p-trifluoromethylphenyl)boron Or it may be triphenylcarboniumtetrapentafluorophenylboron, etc., but is not limited thereto.
[148]
[149]
The catalyst composition may include, as a first method, contacting the transition metal compound represented by Formula 1 with the compound represented by Formula 2 or Formula 3 to obtain a mixture; and adding the compound represented by Formula 4 to the mixture.
[150]
In this case, the molar ratio of the transition metal compound represented by Formula 1 to the compound represented by Formula 2 or 3 may be 1:2 to 1:5,000, specifically 1:10 to 1:1,000, more specifically It may be 1:2 to 1:500.
[151]
When the molar ratio of the transition metal compound represented by Formula 1 to the compound represented by Formula 2 or 3 is less than 1:2, the amount of the alkylating agent is very small, so there is a problem that the alkylation of the metal compound cannot proceed completely, and the molar ratio is When the ratio exceeds 1:5,000, the metal compound is alkylated, but there is a problem in that the alkylated metal compound cannot be completely activated due to a side reaction between the remaining excess alkylating agent and the activator, which is the compound of Formula 4 above.
[152]
In addition, the molar ratio of the transition metal compound represented by Formula 1 to the compound represented by Formula 4 may be 1:1 to 1:25, specifically 1:1 to 1:10, more specifically 1 It may be from :1 to 1:5. When the molar ratio of the transition metal compound represented by Formula 1 to the compound represented by Formula 4 is less than 1:1, the amount of the activator is relatively small, and the activation of the metal compound is not completely achieved, so that the activity of the resulting catalyst composition is decreased. If the molar ratio is greater than 1:25, the metal compound is fully activated, but the cost of the catalyst composition may not be economical or the purity of the resulting polymer may be degraded with an excess of the remaining activator.
[153]
In addition, the catalyst composition may be prepared by contacting the transition metal compound represented by Formula 1 with the compound represented by Formula 2 as a second method.
[154]
In this case, the molar ratio of the transition metal compound represented by Formula 1 to the compound represented by Formula 2 may be 1:10 to 1:10,000, specifically 1:100 to 1:5,000, more specifically 1 :500 to 1:3,000. If the molar ratio is less than 1:10, the amount of the activator is relatively small, so the activation of the metal compound may not be completely achieved, and thus the activity of the resulting catalyst composition may decrease. If it exceeds 1:10,000, the activation of the metal compound may be completely achieved However, the cost of the catalyst composition may not be economical or the purity of the resulting polymer may be deteriorated with the remaining excess activator.
[155]
A hydrocarbon solvent such as pentane, hexane, heptane, or the like or an aromatic solvent such as benzene or toluene may be used as the reaction solvent in the preparation of the catalyst composition, but is not limited thereto.
[156]
In addition, the catalyst composition may include the transition metal compound and the cocatalyst compound in a supported form on a carrier. The carrier may be used without any particular limitation as long as it is used as a carrier in a metallocene-based catalyst. Specifically, the carrier may be silica, silica-alumina or silica-magnesia, and any one or a mixture of two or more thereof may be used.
[157]
Among them, when the carrier is silica, since the functional group of the silica carrier and the metallocene compound of Formula 1 chemically forms a bond, there is almost no catalyst released from the surface during the olefin polymerization process. As a result, it is possible to prevent the occurrence of fouling in which the reactor wall surface or polymer particles are agglomerated during the manufacturing process of the olefin-based copolymer. In addition, the olefin-based copolymer prepared in the presence of the catalyst including the silica carrier is excellent in particle shape and apparent density of the polymer.
[158]
More specifically, the carrier may be high-temperature dried silica or silica-alumina containing a siloxane group having high reactivity on the surface through a method such as high-temperature drying.
[159]
The carrier may further include an oxide, carbonate, sulfate or nitrate component such as Na 2 O, K 2 CO 3 , BaSO 4 or Mg(NO 3 ) 2 .
[160]
The drying temperature of the carrier is preferably 200 to 800°C, more preferably 300 to 600°C, and most preferably 300 to 400°C. When the drying temperature of the carrier is less than 200 ℃, there is too much moisture and the surface moisture and the cocatalyst react. It is undesirable because it disappears and only the siloxane remains, reducing the reaction site with the promoter.
[161]
In addition, the amount of hydroxyl groups on the surface of the carrier is preferably 0.1 to 10 mmol/g, more preferably 0.5 to 5 mmol/g. The amount of hydroxyl groups on the surface of the carrier can be controlled by the method and conditions or drying conditions of the carrier, such as temperature, time, vacuum or spray drying, and the like.
[162]
[163]
The polymerization of the olefin-based copolymer may be performed at a temperature of about 25 to about 500 °C, specifically 50 to 300 °C, more preferably 50 to 250 °C, or 50 to 200 °C.
[164]
In addition, the polymerization of the olefin-based copolymer is 1 kgf/cm 2 to 150 kgf/cm 2 A pressure of, preferably 1 kgf/cm 2 to 120 kgf/cm 2 , more preferably 5 kgf/cm 2 to 100 It can be carried out at a pressure of kgf/cm 2 .
[165]
[166]
The polymerization reaction of the olefinic monomer may be performed under an inert solvent, and examples of the inert solvent include benzene, toluene, xylene, cumene, heptane, cyclohexane, methylcyclohexane, methylcyclopentane, n-hexane, and 1-hexene. , 1-octene, but not limited thereto.
[167]
[168]
The olefin-based copolymer of the present invention may be usefully used in the manufacture of a molded article. Specifically, the molded article may be a blow molding molded article, an inflation molded article, a cast molded article, an extrusion laminate molded article, an extrusion molded article, an expanded molded article, an injection molded article, a sheet, a film, a fiber, a monofilament, or a nonwoven fabric, etc. not limited
[169]
[170]
Example
[171]
Hereinafter, the present invention will be described in more detail by way of Examples. However, the following examples are provided to illustrate the present invention, and the scope of the present invention is not limited thereto.
[172]
[173]
Preparation Example 1
[174]

[175]
Synthesis of N-tert-butyl-1-(1,2-dimethyl-3H-benzo[b]cyclopenta[d]thiophen-3-yl)-1,1-dimethylsilanamine
[176]

[177]
After quantitatively adding 4.65 g (15.88 mmol) of the compound of Formula 3 to a 100 ml Schlenk flask, 80 ml of THF was added thereto. After adding tBuNH 2 (4eq, 6.68ml) at room temperature, the reaction was conducted at room temperature for 3 days. After the reaction, THF was removed and then filtered with hexane. After solvent drying, a yellow liquid was obtained in a yield of 4.50 g (86%).
[178]
1 H-NMR (in CDCl 3 , 500 MHz): 7.99 (d, 1H), 7.83 (d, 1H), 7.35 (dd, 1H), 7.24 (dd, 1H), 3.49 (s, 1H), 2.37 ( s, 3H), 2.17 (s, 3H), 1.27 (s, 9H), 0.19 (s, 3H), -0.17 (s, 3H).
[179]

[180]

[181]
In a 50ml Schlenk flask, the above formula 2-1 ligand compound (1.06g, 3.22mmol/1.0eq) and MTBE 16.0mL (0.2M) were put and stirred first. n-BuLi (2.64ml, 6.60mmol/2.05eq, 2.5M in THF) was added at -40 o C, and the reaction was carried out at room temperature overnight. After that, MeMgBr (2.68ml, 8.05 mmol/2.5eq, 3.0M in diethyl ether) was slowly added dropwise at -40 o C, and TiCl 4 (2.68ml, 3.22 mmol/1.0eq, 1.0M in toluene) was added in this order. and reacted overnight at room temperature. Then, the reaction mixture was filtered through Celite using hexane. After solvent drying, a brown solid was obtained in a yield of 1.07 g (82%).
[182]
1 H-NMR (in CDCl 3 , 500 MHz): 7.99 (d, 1H), 7.68 (d, 1H), 7.40 (dd, 1H), 7.30 (dd, 1H), 3.22 (s, 1H), 2.67 ( s, 3H), 2.05 (s, 3H), 1.54 (s, 9H), 0.58 (s, 3H), 0.57 (s, 3H), 0.40 (s, 3H), -0.45 (s, 3H).
[183]
[184]
Comparative Preparation Example 1
[185]

[186]
Synthesis of N-tert-butyl-1-(1,2-dimethyl-3H-benzo[b]cyclopenta[d]thiophen-3-yl)-1,1-(methyl)(phenyl)silanamine
[187]

[188]
(i) Preparation of chloro-1-(1,2-dimethyl-3H-benzo[b]cyclopenta[d]thiophen-3-yl)-1,1-(methyl)(phenyl)silane
[189]
In a 250 ml Schlenk flask, put 10 g (1.0 eq, 49.925 mmol) of 1,2-dimethyl-3H-benzo [b] cyclopenta [d] thiophene and 100 ml of THF, and 22 ml of n-BuLi (1.1 eq, 54.918 mmol, 2.5 M in hexane) was added dropwise at -30 °C, followed by stirring at room temperature for 3 hours. The stirred Li-complex THF solution was cannulated at -78 °C in a Schlenk flask containing 8.1 ml (1.0 eq, 49.925 mmol) of dichloro(methyl)(phenyl)silane and 70 ml of THF, followed by stirring at room temperature overnight. After stirring, the mixture was dried in vacuo, and extracted with 100 ml of hexane.
[190]
(ii) N-tert-butyl-1-(1,2-dimethyl-3H-benzo[b]cyclopenta[d]thiophen-3-yl)-1,1-(methyl)(phenyl)silanamine Produce
[191]
t-BuNH in 100 ml of extracted chloro-1-(1,2-dimethyl-3H-benzo[b]cyclopenta[d]thiophen-3-yl)-1,1-(methyl)(phenyl)silane hexane solution 2 42 ml (8 eq, 399.4 mmol) was added at room temperature, followed by stirring at room temperature overnight. After stirring, the mixture was dried in vacuo, and extracted with 150 ml of hexane. After solvent drying, 13.36 g (68 %, dr = 1:1) of a yellow solid was obtained.
[192]
1 H NMR (CDCl 3 , 500 MHz): δ 7.93 (t, 2H), 7.79 (d,1H), 7.71 (d,1H), 7.60 (d, 2H), 7.48 (d, 2H), 7.40-7.10 (m, 10H, aromatic), 3.62 (s, 1H), 3.60 (s, 1H), 2.28 (s, 6H), 2.09 (s, 3H), 1.76 (s, 3H), 1.12 (s, 18H), 0.23 (s, 3H), 0.13 (s, 3H)
[193]

[194]

[195]
In a 100 ml Schlenk flask, put 4.93 g (12.575 mmol, 1.0 eq) of the ligand compound prepared above and 50 ml (0.2M) of toluene, and 10.3 ml (25.779 mmol, 2.05 eq, 2.5M in hexane) of n-BuLi - After dropwise addition at 30°C, the mixture was stirred at room temperature overnight. After stirring, 12.6 ml of MeMgBr (37.725 mmol, 3.0 eq, 3.0 M in diethyl ether) was added dropwise, and then 13.2 ml of TiCl 4 (13.204 mmol, 1.05 eq, 1.0 M in toluene) was added in order and stirred at room temperature overnight. . After stirring, the mixture was dried in vacuo, extracted with 150 ml of hexane, and the solvent was removed to 50 ml, and then 4 ml (37.725 mmol, 3.0eq) of DME was added dropwise, followed by stirring at room temperature overnight. After vacuum drying again, the mixture was extracted with 150 ml of hexane. After solvent drying, 2.23 g (38 %, dr = 1:0.5) of a brown solid was obtained.
[196]
1 H NMR (CDCl 3 , 500 MHz): δ 7.98 (d, 1H), 7.94 (d, 1H), 7.71 (t, 6H), 7.50-7.30 (10H), 2.66 (s, 3H), 2.61 (s) , 3H), 2.15 (s, 3H), 1.62 (s, 9H), 1.56 (s, 9H), 1.53 (s, 3H), 0.93 (s, 3H), 0.31 (s, 3H), 0.58 (s, 3H), 0.51 (s, 3H), -0.26 (s, 3H), -0.39 (s, 3H)
[197]
Example 1
[198]
After the 1.5L autoclave continuous process reactor was charged with hexane solvent (7 kg/h) and 1-butene (0.95 kg/h), the temperature at the top of the reactor was preheated to 141 °C. Triisobutylaluminum compound (0.05 mmol/min), the transition metal compound (0.17 μmol/min) obtained in Preparation Example 1 as a catalyst, and dimethylanilinium tetrakis (pentafluorophenyl) borate cocatalyst (0.51 μmol/min) ) were simultaneously introduced into the reactor. Then, ethylene (0.87 kg/h) hydrogen gas (12 cc/min) was introduced into the autoclave reactor and maintained at 141° C. for at least 30 minutes in a continuous process at a pressure of 89 bar to proceed with copolymerization to obtain a copolymer. got it After drying for more than 12 hours, the physical properties were measured.
[199]
Examples 2 to 5
[200]
A copolymer was prepared in the same manner as in Example 1, except that the reaction conditions were changed as shown in Table 1 below.
[201]
Comparative Examples 1 and 2
[202]
As Comparative Example 1, DF7350 (Mitsui Corporation) was purchased and used, and as Comparative Example 2, EG8137 (Dow Corporation) was purchased and used.
[203]
Comparative Examples 3 and 4
[204]
Comparative Example 3 uses the catalyst of Preparation Example 1, but the content of the material is changed as shown in Table 1 below, such as without hydrogen gas, and Comparative Example 4 uses the catalyst of Comparative Preparation Example 1 and the content of other materials Except for the changes as shown in Table 1, a copolymer was prepared in the same manner as in Example 1.
[205]
Comparative Example 5
[206]
As Comparative Example 5, EG8842 (Dow Corporation) was purchased and used.
[207]
[Table 1]
Catalyst type Catalyst content (μmol/min) Cocatalyst (μmol/min) TiBAl (mmol/min) Ethylene (kg/h) Hydrogen (cc/min) Hexane (kg/h) Alpha Olefin Monomer Reaction temperature (℃)
1-butene (kg/h) 1-octene (kg/h)
Example 1 Preparation Example 1 0.17 0.51 0.05 0.87 12 7 0.95 - 141
Example 2 Preparation Example 1 0.17 0.51 0.05 0.87 9 7 0.91 - 141.9
Example 3 Preparation Example 1 0.17 0.51 0.05 0.87 12 7 0.95 - 141.1
Example 4 Preparation Example 1 0.48 1.44 0.1 0.87 8 7 - 1.87 140
Example 5 Preparation Example 1 0.48 1.44 0.1 0.87 8 7 - 1.87 140.2
Comparative Example 1 DF7350
Comparative Example 2 EG8137
Comparative Example 3 Preparation Example 1 0.38 1.14 0.05 0.87 - 5 One - 150
Comparative Example 4 Comparative Preparation Example 1 0.235 0.705 0.05 0.87 23 7 0.85 - 141
Comparative Example 5 EG8842
[208]
Experimental Example 1
[209]
The copolymers of Examples 1 to 5 and Comparative Examples 1 to 4 were evaluated for physical properties according to the following method, and are shown in Table 2.
[210]
1) Density of the polymer
[211]
Measured by ASTM D-792.
[212]
2) Melt Index (MI) of the polymer
[213]
It was measured by ASTM D-1238 (Condition E, 190°C, 2.16 kg load).
[214]
3) Weight average molecular weight (Mw) and molecular weight distribution (MWD)
[215]
The number average molecular weight (Mn) and the weight average molecular weight (Mw) were respectively measured using gel permeation chromatography (GPC), and the molecular weight distribution was calculated by dividing the weight average molecular weight by the number average molecular weight. The weight average molecular weight (Mw) and molecular weight distribution (MWD) measured in this way represent values ​​based on a fraction of the entire polymer prepared above.
[216]
- Column: PL Olexis
[217]
- Solvent: TCB (Trichlorobenzene)
[218]
- Flow rate: 1.0 ml/min
[219]
- Sample concentration: 1.0 mg/ml
[220]
- Injection volume: 200 μl
[221]
- Column temperature: 160℃
[222]
- Detector: Agilent High Temperature RI detector
[223]
- Standard: Polystyrene (corrected by cubic function)
[224]
4) Melting temperature (Tm)
[225]
It was obtained using a differential scanning calorimeter (DSC: Differential Scanning Calorimeter 6000) manufactured by PerKinElmer. That is, after increasing the temperature to 200°C, holding it at that temperature for 1 minute, then lowering it to -100°C, and increasing the temperature again, the top of the DSC curve was used as the melting point. At this time, the rate of temperature rise and fall is 10° C./min, and the melting point is obtained while the second temperature rises.
[226]
5) Elution temperature (Te)
[227]
As the measuring equipment, PolymerChar's CFC was used. First, the polymer solution using o-dichlorobenzene as a solvent was completely dissolved in an oven in a CFC analyzer at 130° C. for 60 minutes, then introduced into a TREF column adjusted to 135° C., cooled to 95° C., and stabilized for 45 minutes. The temperature of the TREF column was then cooled to -20°C at a rate of 0.5°C/min, and then held at -20°C for 10 minutes. Then, the amount of elution (mass %) was measured using an infrared spectrophotometer. Then, the operation of raising the temperature of the TREF column at a rate of 20 °C/min to a preset temperature and maintaining the temperature at the temperature reached for a preset period of time (i.e., about 27 minutes) was performed when the temperature of the TREF was 130 °C. Repeat until this, and the amount (mass %) of the fraction eluted during each temperature range was measured. In addition, the weight average molecular weight (Mw) was measured in the same manner as in the GPC measurement principle, except that the fraction eluted at each temperature was sent to the GPC column and o-dichlorobenzene was used as a solvent.
[228]
The elution temperature (Te) means the temperature corresponding to the highest point in the peak that exists after -20°C when a graph of the temperature versus the elution fraction is drawn.
[229]
6) Determination of soluble fraction (SF) content
[230]
The content of the soluble fraction (SF) refers to the content of the fraction eluted at -20°C or less, and the weight average molecular weight (Mw (SF)) of the soluble fraction was measured using a CFC GPC column.
[231]
7) Weight average molecular weight of soluble fraction (Mw(SF)) and Mw:Mw(SF)
[232]
Mw:Mw(SF) was calculated as the ratio of the weight average molecular weight (Mw) measured by GPC to the weight average molecular weight (Mw(SF)) of the soluble fraction measured by CFC.
[233]
[Table 2]
Density (g/cc) MI (dg/min) Mw MWD Tm (℃) Te (℃) SF (%) Mw(SF) Mw:Mw(SF)
Example 1 0.8698 29.9 44043 2.03 55.6 17.0 5.0 25092 1.8:1
Example 2 0.8721 24.6 53456 2.05 57.8 20.3 4.1 36346 1.47:1
Example 3 0.8709 35.5 41949 2.09 56.2 17.9 5.5 35789 1.17:1
Example 4 0.8674 12.6 65269 2.14 57.4 19.9 2.9 34750 1.9:1
Example 5 0.8651 18.0 57700 2.2 56.4 17.9 3.8 39761 1.45:1
Comparative Example 1 0.8700 29.5 44489 1.91 53.9 18.2 4.4 9877 4.5:1
Comparative Example 2 0.8700 30.3 47495 2.12 53.6 17.6 4.6 10481 4.5:1
Comparative Example 3 0.8702 28.3 45016 1.96 55.9 17.3 4.8 5587 8.1:1
Comparative Example 4 0.8690 12.5 63581 2.04 61.1 23.3 3.3 20800 3.1:1
Comparative Example 5 0.8590 0.95 132023 2.02 43.1 7.7 5.3 135552 0.97:1
[234]
As shown in Table 2, in the case of Examples 1 to 5, in which the olefin-based copolymer was prepared by adding hydrogen while using the transition metal compound of Formula 1, the weight average molecular weight of the soluble fraction was 22,000 or more, and a high value was shown. , and at the same time, the ratio with the total weight average molecular weight of the olefin-based copolymer was also 1:1 to 2: 1, and it was found that the weight average molecular weight of the soluble fraction was similar to the total weight average molecular weight.
[235]
On the other hand, in Comparative Examples 1 and 2, which are conventional copolymers that are commercially available, Comparative Example 3 polymerized without hydrogen input, and Comparative Example 4 using the catalyst of Comparative Preparation Example 1 that does not correspond to Chemical Formula 1, the weight of the soluble fraction It can be seen that the average molecular weight is less than 22,000, and the ratio with the weight average molecular weight of all olefin-based copolymers also shows a large difference from 3.1:1 to 8.1:1.
[236]
In particular, as in Comparative Example 5, if the ratio of the weight average molecular weight of the soluble fraction to the total weight average molecular weight was increased, it was confirmed that it was difficult to maintain the melt index as high as 10 or more at the same time.
[237]
Experimental Example 2
[238]
For the olefinic copolymers of Examples 1 and 4 and Comparative Examples 1 to 4, tear strength, tensile strength, elongation, flexural strength, and hardness were measured according to the following method, and are shown in Table 3 below.
[239]
1) Tear strength, tensile strength, elongation
[240]
Each of the olefin-based copolymers was extruded to prepare pellets, and then measured according to ASTM D638 (50 mm/min).
[241]
2) Flexural strength
[242]
Measured according to ASTM D790.
[243]
3) Hardness (shore A)
[244]
Hardness was measured according to ASTM D2240 standard using TECLOCK's GC610 STAND for Durometer and Mitutoyo's Shore Durometer Type A.
[245]
[Table 3]
Tear strength (kN/m) Tensile strength (MPa) Elongation (%) Flexural strength (MPa) Hardness
Example 1 25.3 22.5 > 400 8.9 66.3
Comparative Example 1 24.1 21.6 > 400 7.8 66.1
Comparative Example 2 23.8 22.6 > 400 8.0 64.7
Comparative Example 3 23.0 20.2 > 400 6.9 64.2
[246]
[Table 4]
Tear strength (kN/m) Tensile strength (MPa) Elongation (%) Flexural strength (MPa) Hardness
Example 4 32.64 4.47 1200 12.4 61.16
Comparative Example 4 29.49 4.27 1200 12.2 58.5
[247]
As summarized in Table 2, the olefinic copolymers of Example 1 and Comparative Examples 1 to 3 exhibited melt index values ​​at a similar level. However, in Example 1, the Mw (SF) value is 22,000 or more and the Mw: Mw (SF) value is 1.8: 1, which satisfies all of the conditions (a) to (c), whereas in Comparative Examples 1 to 3, There is a difference in that the Mw(SF) value is less than 11,000 and the Mw:Mw(SF) value is 4.5:1 or 8:1, which does not satisfy the conditions (b) and (c).
[248]
Similarly, the olefinic copolymers of Example 4 and Comparative Example 4 show similar melt index values. In Example 4, the Mw (SF) value is 34,750 and the Mw: Mw (SF) value is 1.9: 1 Then, all of the conditions (a) to (c) are satisfied, but in Comparative Example 4, the Mw(SF) value is less than 22,000 and the Mw: Mw(SF) value is 3.1:1, so that the conditions (b) and (c) are There are differences that are not satisfied.
[249]
Comparing based on the above contents, as shown in Table 3, the olefinic copolymer of Example 1 exhibits the same level of elongation as compared to the copolymers of Comparative Examples 1 to 3, while exhibiting the same level of elongation, tear strength, tensile strength, and flexure. Physical properties such as strength and hardness are excellent. Similarly, as shown in Table 4, the olefin-based copolymer of Example 4 has physical properties such as tear strength, tensile strength, flexural strength, and hardness than the olefin-based copolymer of Comparative Example 4 This improvement was confirmed.
[250]
That is, the olefin-based copolymer of the present invention has a melt index of 10 to 100 g/10 min and the weight average molecular weight and ratio of the soluble fraction at -20 ° C. It was found that all physical properties such as tear strength and tensile strength were excellent.
Claims
[Claim 1]
Olefin-based copolymers satisfying the following conditions (a) to (c): (a) Melt Index (MI, 190° C., 2.16 kg load condition) is 10 to 100 g/10 min, (b) cross fractionation The soluble fraction (SF) at -20 °C measured by cross-fractionation chromatography (CFC) is 0.5 to 10 wt%, and the weight average molecular weight (Mw (SF)) of the soluble fraction is 22,000 or more and (c) the ratio of the weight average molecular weight (Mw) of the olefin-based copolymer to the weight average molecular weight (Mw (SF)) of the soluble fraction Mw: Mw (SF) has a value of 0.9: 1 to 2: 1. .
[Claim 2]
The method according to claim 1, The weight average molecular weight (Mw) of the olefin-based copolymer is 10,000 g / mol to 100,000 g / mol, the olefin-based copolymer.
[Claim 3]
The method according to claim 1, The molecular weight distribution of the olefin-based copolymer is 1.5 to 3.0, the olefin-based copolymer.
[Claim 4]
The olefin-based copolymer according to claim 1, wherein the olefin-based copolymer is a copolymer of ethylene and an alpha-olefin comonomer having 3 to 12 carbon atoms.
[Claim 5]
5. The method of claim 4, wherein the alpha-olefin comonomer is propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-heptene, 1-octene, 1-decene, 1-undecene , 1-dodecene, 1-tetradecene, 1-hexadecene, 1-eicosene, norbornene, norbornadiene, ethylidenenorbornene, phenylnorbornene, vinylnorbornene, dicyclopentadiene, 1,4- An olefin-based copolymer comprising at least one selected from the group consisting of butadiene, 1,5-pentadiene, 1,6-hexadiene, styrene, alpha-methylstyrene, divinylbenzene and 3-chloromethylstyrene.
[Claim 6]
In the presence of a catalyst composition comprising a transition metal compound represented by the following formula (1), by introducing hydrogen at 10 to 100 cc / min to polymerize the olefinic monomer; Preparation of the olefinic copolymer of claim 1, including: Method: [Formula 1] In Formula 1, R 1 is hydrogen; alkyl having 1 to 20 carbon atoms; alkenyl having 2 to 20 carbon atoms; alkoxy having 1 to 20 carbon atoms; aryl having 6 to 20 carbon atoms; arylalkoxy having 7 to 20 carbon atoms; alkylaryl having 7 to 20 carbon atoms; or arylalkyl having 7 to 20 carbon atoms, and R 2 and R 3 are each independently hydrogen; halogen; alkyl having 1 to 20 carbon atoms; alkenyl having 2 to 20 carbon atoms; arylalkyl having 7 to 20 carbon atoms; alkylamido having 1 to 20 carbon atoms; or arylamido having 6 to 20 carbon atoms, and R 4 to R 9 are each independently hydrogen; silyl; alkyl having 1 to 20 carbon atoms; alkenyl having 2 to 20 carbon atoms; aryl having 6 to 20 carbon atoms; alkylaryl having 7 to 20 carbon atoms; arylalkyl having 7 to 20 carbon atoms; or a metalloid radical of a Group 14 metal substituted with hydrocarbyl having 1 to 20 carbon atoms, wherein R 2 to R 9two or more adjacent to each other may be connected to each other to form a ring, Q is Si, C, N, P or S, M is a Group 4 transition metal, X 1 and X 2 are each independently hydrogen; halogen; alkyl having 1 to 20 carbon atoms; alkenyl having 2 to 20 carbon atoms; aryl having 6 to 20 carbon atoms; alkylaryl having 7 to 20 carbon atoms; arylalkyl having 7 to 20 carbon atoms; alkylamino having 1 to 20 carbon atoms; or arylamino having 6 to 20 carbon atoms.
[Claim 7]
The method according to claim 6, wherein R 1 Is hydrogen; alkyl having 1 to 20 carbon atoms; alkoxy having 1 to 20 carbon atoms; aryl having 6 to 20 carbon atoms; arylalkoxy having 7 to 20 carbon atoms; alkylaryl having 7 to 20 carbon atoms; or arylalkyl having 7 to 20 carbon atoms, wherein R 2 and R 3 are each independently hydrogen; alkyl having 1 to 20 carbon atoms; aryl having 6 to 20 carbon atoms; or an alkylaryl having 6 to 20 carbon atoms, wherein R 4 to R 9 are each independently hydrogen; alkyl having 1 to 20 carbon atoms; aryl having 6 to 20 carbon atoms; alkylaryl having 7 to 20 carbon atoms; or arylalkyl having 7 to 20 carbon atoms, and two or more adjacent to each other among R 2 to R 9 may be connected to each other to form an aliphatic ring having 5 to 20 carbon atoms or an aromatic ring having 6 to 20 carbon atoms, the aliphatic The ring or aromatic ring may be substituted with halogen, alkyl having 1 to 20 carbons, alkenyl having 2 to 20 carbons, or aryl having 6 to 20 carbons, wherein Q is Si, C, N or P, olefinic public A method for producing a composite.
[Claim 8]
The method according to claim 6, wherein R One Is alkyl having 1 to 20 carbon atoms; aryl having 6 to 20 carbon atoms; arylalkoxy having 7 to 20 carbon atoms; or arylalkyl having 7 to 20 carbon atoms, wherein R 2 and R 3 are each independently hydrogen; alkyl having 1 to 20 carbon atoms; or aryl having 6 to 20 carbon atoms, wherein R 4 to R 9 are each independently hydrogen; alkyl having 1 to 20 carbon atoms; or aryl having 6 to 20 carbon atoms, and Q is Si.
[Claim 9]
The method of claim 6, wherein the transition metal compound represented by Chemical Formula 1 is selected from the group consisting of compounds of Chemical Formulas 1-1 to 1-6. [Formula 1-1] [Formula 1-2] [Formula 1-3] [Formula 1-4] [Formula 1-5] [Formula 1-6]
[Claim 10]
The method of claim 6, wherein the polymerization is carried out at 50 to 200 °C.